Unsymmetrical n, n&#39;-(n, nu-disubstituted aminoalkyl)-hydrazines



3,098,073 UNSYMMETRICAL N ,N-(N,N-DEUBTITUTED AMlNOALKYL)-HYDRAZINESJohn H. Biol, Milwaukee, Wis, assignor, by mesne assignments, toLakeside Laboratories, Inc, Milwaukee,

Wis, a corporation of Delaware No Drawing. Filed Jan. 13, 19%, Ser. No.2,123 8 Claims. (Cl. 269-4475) ire as well as acid addition salts andquaternary ammonium salts thereof, wherein A is a member of the groupconsisting of CH -NHN= CH--(CH and (CHz) m-NNH (CH2) n+1- wherein m isan integer from 2 to 10, n is an integer from 1 to 9, R is a member ofthe group consisting of hydrogen and lower alkyl groups, and

R and R represent members of the group consisting of lower alkyl,phenyl, phenyl-lower alkyl, monocyclic alkyl, lower alkenyl and loweralkynyl, and

N- and -N R2 R4 represent nonidentical members of the group consistingof morpholino, pyrrolidino, piperidino, 1,2,3,4-tetrahydroisoquinolino,1,2,3,4-tetrahydroquinolino, isoindolino, 4- lower alkyl-l-piperazino,3-hydroXypipe1-idino, 4-hydroxypiperidino, indolino, theophyll ino andphenot hiazino,

R is lower alkyl, R, and R are members of the group consisting ofphenyl, phenyl-lower alkyl, monocyclic alkyl, lower alkenyl, loweralkynyl and lower alkyls, at least one of 3,098,073 Patented July 16,1963 ice said lower alkyls being different than the lower alkylrepresented by R R is phenyl,

R and R are members of the group consisting of phenyl-lower alkyl,monocyclic alkyl, lower alkenyl and lower alkynyl,

R is phenyl-lower alkyl,

R and R are members of the group consisting of monocyclic alkyl, loweralkenyl and lower alkynyl,

R is lower alkyl,

F R and R are members of the group consisting of phenyl, phenyl-loweralkyl, monocyclic alkyl, lower alkenyl and lower alkynyl,

R is phenyl-lower alkyl, and

R R and R are members of the group consisting of phenyl, monocyclicalkyl, lower alkyl, lower alkenyl and lower alkynyl, and nontoxic acidaddition salts, and nontoxic quaternary ammonium salts thereof derivedfrom compounds in which the organic moiety is a member of the groupconsisting of lower alkyl, phenyl-lower alkyl and lower alkynyl groups.

Typical lower alkyl groups represented by R R R R R R R R20, R and R aremethyl, ethyl, propyl, butyl, pentyl and hexyl.

Typical lower alkenyl groups represented by R R 7 8 10 11 13, 14, R16,17 and R18 are the allyl group and the 1-(2-butenyl) group.

Typical pheny'l-lower alkyl groups represented by R 2 7, 8 10, 11 12 R1617, R18 and 19 are y phenylethyl, and phenylpropyl.

Although 1, 2, 7, 3 9, 16, 17, R18: 20 21 and R are shown to representphenyl, this is intended to include the nuclear substituted phenylgroups such as hydroxyphenyl, lower alkoxyphenyl groups such asmethoxyphenyl, hallophenyl groups such as chlorophenyl and loweracyloxyphenyl groups in which the acyloXy is from a lower aliphaticmonocarboxylic acid such as acetoxyphenyl.

Typical monocyclic alkyl groups represented by R R 7 8, 10 11 13, 14,R16 17 R18 20 21 and 22 are the cyclopentyl and cyclohexyll groups.

Typical alkynyl groups represented by R R R R 10, 11, 13 14, R16: 17,18, 20 21 and 22 are propynyl and butynyl.

Of especial importance for the uses hereinafter described are thecompounds of the formula R1 R3 NA-N R3 R4 wherein R R R R and A have thesignificance hereinabove assigned, as well as the compounds wherein Rand A have the significance assigned and R and R are lower alkyls, atleast one of which is difierent than the lower alkyl represented by RThe most important compounds of the group as hypotensive agents arethose of the formula wherein A has the significance previously assigned,R and R are both lower alkyls, and

represents pyrrolidino, piperidino, 4-lower alkyl-piperazino,morpholino, 3-hydroxypiperidino and 1,2,3,4-tetrahydroisoquinolino.

Compounds of the above formulae are conveniently produced by reacting amono N-(disubstituted aminoa1ky1)- hydrazine with an N,N-disubstitutedaminoalkyl aldehyde to produce an intermediate unsymmetricalN-(disubstituted aminoalkyl)-N-(disubstituted aminoalkylidenyl)hydrazineand reducing the hydrazone to the corresponding hydrazine. This processmay be represented as follows with particular regard to the productionof the compounds having the groups represented by R R R and R wherein m,n, R R R and R have the significance I previously assigned. The othercompounds with different substituents on the terminal nitrogens can beproduced in the same way.

The amino N-(disubstituted aminoalkyl)hydrazines used as startingmaterials may be produced according to the processes shown in mycopending application Serial No. 679,520, filed August 21, 1957, and nowabandoned. Representative of such reactants are dimethylaminoethylhydraxine, 'y-di-isopropylaminobutyl hydrazine, pyrrolidinoethylhydrazine, morpholinoethyl hydrazine, 'y-( 1-methyl-4-piperazino)-propyl hydrazine, B-(N-benzyD- methylaminoethylhydrazine, B-(N-o-chlorobenzyl)-methylaminoethyl hydrazine,,6-(3-hydroxypiperidino)-ethyl hydrazine, fl-1,2,3,4-tetrahydroisoquinolino)-ethyl hydrazine and fl-theophyllinoethylhydrazine, N-allyl methylaminoethyl hydrazine, N-propargylethylaminopropyl hydrazine, N-cyclopentyl methylaminobutyl hydrazine, N-cyclohexenyl n-propylaminoethyl hydrazine, N-(p-methoxyphenyl) isopropylN-fi-phenethylaminobuty'l hydrazine,N-o-chlorobenzyl-N-Z-phenoxy-ethylaminoethyl hydraZine,N,N-dibenzylaminoethyl hydrazine, 2-[N-(2- chloroethyl)-N-methyl]-aminomethy1 benzodioxan hydra; zine,N-1-naphthylmethyl-N-ethylaminoethyl hydrazine,N-Z-pyridyl-N-benzylarrtinoethyl hydrazine, N-2-pyridyl-N-p-methoxybenzylaminoethyl hydrazine, N-Z-biphenyloxyethylmethylaminoethyl hydrazine, Z-indolinoethyl hydrazine,S-indolinoisopropyl hydrazine,N-(p-hydroxyphenylisopropyl)-N-methylaminoethyl hydrazine,N-(mmethoxyphenylethyl)-N-methylaminoethyl hydrazine, N-2-pyrimidyl-N-methylaminopropyl hydrazine and the like.

Examples of the N-N-disubstituted aminoalkyl aldehydes and acetalsthereof which may be used are dimethylaminoacetaldehyde,diethylaminoacetaldehyde, N-pyrrolidinoacetaldehyde,N-morpholinoacetaldehyde, N-1,2,3,4-tetrahydroisoquinolino-acetaldehyde,N- isoindo'lino-acetaldehyde, 3-hydroxypiperidino-acetaldehyde,N-4-hydroxypiperidinoacetaldehyde, N-3-phenoxypiperidinoacetaldehyde,diphenylaminopropionaldehyde, dibenzylaminobutyraldehyde,

5- (N-phenyl-N-ethylamino) valeraldehyde, 8-morphol-ino caprylaldehyde,dimethylam inoacetal,

diethylaminoaceta l, 3-dimethylaminopropionaldehyde,

N-rnethyl-N-o-chlorobenzylaminoacetal,

pyrrolidino-acetal,

1-methyl-4-piperazinoacetal,

4- [N-p-methoxybenzyl-N-methyl amino] -butyraldehyde,

N-propagry'l ethylaminopropionaldehyde,

3-thiophy1lino-aceta1dehyde,

N-allyl methylaminoacetaldehyde,

diallylaminoacetaldehyde,

dicyclopentyiaminobutyraldehyde,

dicyclohexylaminopropionaldehyde,

dibenzylaminoacetaldehyde,

N-l-naphthyl methyl-N-ethylaminoacetaldehyde,

N-Z-pyr-idyl-N-benzylaminopropionaldehyde,

N-2-pyridyl-N-p-methoxybenzylaminobutyraldehyde,

N-Z-biphenyloxyethyl methylaminoacetaldehyde,

3-indolylacetaldehyde,

3-indolylisopropionaldehyde,

N-(p-hydroxyphenylisopropyl) -N-methylaminoacetaldehyde,

N- (m-methoxyphenylethyl) -N-methylaminoacetaldehyde, and

N-Z-pyrimidyl-N-methylaminobutyraldehyde.

Reaction of an N,N-(disubstituted aminoalkyD-aldehyde with amono-N-(disubstituted aminoalkyl)-hydrazinc is conveniently eifected bycontacting the reactants, preferably equimolar quantities thereof, inthe presence of water. The reaction proceeds at room temperaturealthough slightly elevated temperatures may be employed to increase therate of reaction. At room temperature, about 5 to 20 hours is adequateto substantially complete the reaction. Recovery of the desiredaminoalkylidenyl hydrazine is conveniently achieved by conventionalmethods. Thus, the products, generally oils as the free base, may besalted out with an alkali metal hydroxide and extracted with a waterimmiscible organic solvent such as ether. The product is readilyisolated by distillation under reduced pressure.

The N,N-disubstituted aminoalkyl aldehydes may be employed in thereaction as the free aldehydes or as the corresponding acetals. Acetalsare preferably employed when the free aldehydes are not of significantstability. To achieve reaction when an acetal is used, a strong acidshould be present in the reaction mixture to hydrolyze the acetal to thealdehyde in situ; the excess acid is neutralized prior to reaction withthe hydrazine.

Among the N-(disubstituted aminoalkyl)-N-(disubstitutedaminoalkylidenyl)-hydrazines which are produced according to thedescribed process are N 2-pyrrolidinoethyl) -N-(Z-dimethylaminoethylidenyl) -hydrazine,

N- Z-piperidinoethyl -N- (Z-dibutylaminopropylidenyl hydrazine,

N- (4-0-chlorobenzylmethylaminobutyl -N'- Z-piperidinoethylidenyl)-hydrazine,

N- [2-( 1,2,3,4-tetrahydroisoquinolino) ethyl] -N'- [2-( 1-methy1-4-piperazine)-ethylidenyl]-hydrazine,

N- [3-(N-methy1-N-a'llyl) -arrrinopropyl] -N- 2-isoindolinoethylidenyl-hydrazine,

N- [2(p-methoxybenzyl) methylaminoethyl] -N'-2 dimethylaminoethylidenyl-hydrazine,

N- [2- o-methylbenzyl) -rnethylaminoethyl] -N-( 2-d-imethylaminoethylidenyl hydrazine,

N- 2-N-cyclohexyl-N-methylaminoethyl -N'- (Z-diethylaminoethylidenylhydrazine,

N-[ (2-benzodioxyl) -ethylaminoethyl] -N'- (Z-dimethylarninoethylidenyl)-hydrazine,

N- 3-diallylaminopropyl) -N-(4-dimethylaminobutylidenyl) hydrazine,

N- diphenylaminoethyl) -N'- dibenzylaminoethylidenyl -hydrazine,

N-dicyclohexylaminopentyl -N'-(dipropargylaminobutylidenyl) -hydrazine,

N- dipropylaminoethyl) -N- dimethylaminoethylidenyl) -hydrazine,

N- (methyleflhylam inopropyl) -N'-( dipropylaminoethylidenyl hydrazine,

N-(morpholinoethyl) -N'- piperidinopropylidenyl) hydrazine,

N-( 1,2,3,4-tetrahydroquinolinoethyl) -N'- (morpholinoethylidenyl)-hydrazine,

N- 6- 3 -hydroxypiperidinohexyl) 1 -N- [2- (indolinoethyl) hydrazine.

N-( 2-theophyl linoethyl) -N'-( 4-phenothiazinobutyl) hydrazine and N-2-phernothiazinoethyl) -N'- 6-theophyllinohexyl hydrazine, and the like.

The N-(disubstituted aminoalkyl)-N-(disubstitutedaminoalkylidenyl)-hydrazines can be reduced to the correspondinghydrazines by use of a suitable reducing agent. Lithium aluminum hydrideis the preferred reducing agent although others can be used such ascatalytic hydrogenation. Catalytic processes, however, sometimes cleavethe hydrazine bond. With lithium aluminum hydride, the reduction may beconveniently effected by intimately combining the reactants in an inertorganic solvent such as anhydrous ether, dioxane and tetrahydrofuran.Elevated temperatures such as the reflux temperature enhance thereaction. At reflux temperature, from 1 to 8 hours is usually sufiicientto substantially complete the reaction. After the reaction isterminated, water may be added to the mixture to decompose excesslithium aluminum hydride. To recover the product, the organic phase isseparated and the aqueous residue extracted with the same solvent. Theorganic phase and extracts then may be combined, dried, and the productdistilled.

Hydrazines, such as those from the hydrazones named above, may be formedin this way.

The unsymmetrical N,N'-(N,N-disubstituted aminoalkyl)-hydrazines can besubstituted at the N or N'-position by suitable means. Thus, suchcompounds may be methylated by reaction with formaldehyde or an alkylformate and subsequent reduction of the intermediate formyl group with areducing agent to form a methyl group.

This reaction may be represented as follows with particular regard tothe production of the compounds having the groups represented by R R Rand R wherein m, n, R R R and R have the significance previouslyassigned. The other compounds with different substituents on theterminal nitrogens can be produced in the same way.

To effect the reaction the hydrazine may be added to an inert solventsuch as ether or tetrahydrofuran, formaldehyde or an alkylformate suchas ethyl formate, and then a reducing agent such as lithium aluminumhydride added to the mixture. In this wayN-(Z-dimethylaminoethyl)-N-(2-pyrrolidinoethyl)-hydrazine as well as theother hydrazines, may be methylated to form N-(2-dimethaminoethyl)-N orN-methyl-N-(2-pyrrolidinoethy1)-hydraz.ine.

Acid addition salts and quaternary ammonium salts of the hydrazones andhydrazines are also provided. By reacting a hydrazone or hydrazine witha mineral or organic acid an acid addition salt is produced. Acids suchas hydrochloric, sulfuric, formic, acetic, citric, maleic, fumaric andphosphoric may be used to form salts. For each mole of base, there canbe reacted 1 to 3 mole equivalents of acid.

Quaternary ammonium salts are readily produced by combining a hydrazineor hydrazone with a suitable alkylating agent such as an alkyl oraralkyl ester of an acid and particularly dimethyl sulfate, methylchloride, ethyl bromide, methyl iodide, o-chlorobenzyl bromide, phenylethyl chloride, phenylpropyl bromide, benzyl chloride, propargylchloride and equivalents thereof.

Both the acid addition salts and quaternary ammonium salts form at roomtemperature although slightly elevated temperatures may be used toincrease the reaction. The salts precipitate readily from most organicsolvents; some selection of solvent may be necessary but this is withinthe skill of the art.

The nontoxic bis-quaternary ammonium salts of the hydrazines are usefulas ganglionic blocking agents while the nontoxic acid addition salts ofthe hydrazines are useful as diuretics. The onium salts also havehypotensive activity of long duration and thus can be used to lowerblood pressure in animals. The compounds can be administered orally.

The free bases are also useful in the isolation and purification ofpenicillin with which they form salts.

The following examples are presented to illustrate, but not limit, theinvention.

EXAMPLE 1 N-Dimethylcflm-inoethyl-N-Pyrr0lidin0ethylidenyl Hydrazine Amixture containing 46.7 gm. (0.25 mole) of pyrrolidinoacetal and 250 gm.of concentrated hydrochloric acid was allowed to stand for 16 hours. Thereaction mixture was concentrated to dryness in vacuo and the residuedissolved in 200 ml. of water. The pH of the solution was adjusted to 7with 20% sodium hydroxide. A solution containing 20.6 gm. (0.2 mole) ofZ-dimethylaminoethyl hydrazine was added to the above mixture and theresulting solution allowed to stand for 16 hours. The reaction mixturewas made strongly alkaline with solid potassium hydroxide and theproduct extracted from the alkaline solution with ether. The etherextracts were dried with anhydrous potassium carbonate. The ether wasremoved by distillation and the product collected at 105 C. (0.9 mm).Yield, 26.5 gm. (67%); N 1.4936.

Analysis.-Calcd. for C H N N, 14.13 (for 2 titratable nitrogen atoms).Found: N, 14.43.

EXAMPLE 2 N-Dimethylaminoeflzyl-N'-Pyrr0lidin0ethyl Hydrazine To 3.4 gm.(0.09 mole) of lithium aluminum hydride in 200 cc. of dry ether wasadded a solution of 19.5 gm. (0.1 mole) of the ethylidene derivativeproduced as in Example 1 in 100 cc. of dry ether. The mixture wasstirred at room temperature for 5 hours and the complex decomposed bythe addition of 20 cc. of 40% potassium hydroxide solution. The etherlayer was decanted, the solid residue washed repeatedly with additionalether and the combined ether extracts dried with potassium carbonate.The ether was removed by distillation and the product collected at 99 C.(0.8 mm.). Yield, 14.5 gm. (73%); N 1.4870.

Analysis.Calcd. for C H N N (titratable), 13.98. Found: N, 14.12.

7 EXAMPLE 3 N-(3-Hydr0xypiperidino)Ethyl-N-Dimethylaminoethyl HydrazineThis compound was prepared from 3-hydroxypiperidinoacetal anddimethylaminoethyl hydrazine by the procedure of Examples -1 and 2 withthe exception that the ethylidene derivative was not purified bydistillation but was reduced immediately in tetrahydrofuran; B.P. 145-150 (0.05 mm.). Yield, 55.4%; N 1.5041.

Analysis.Calcd. for C H N N (titratable), 18.24. Found: N, 14.47.

EXAMPLE 4 N-(3-Hydroxypiperidino)-Ethylidenyl-N- PyrrolidinoethylHydrazine This compound was prepared from 3-hydroxypiperi-. dinoaectaland pyrrolidinoethyl hydrazine as per Examples land 2; B.P. 100 C. (0.3mm.). Yield, 76%; N 1.5111.

Analysis.Calcd. for C H N N (titratable), 11.06. Found: N, 12.10.

EXAMPLE 8 N -Dimethylaminethyl-N 1 ,2 ,3 ,4- Tetrahya'rois0quin0lino)Ethyl Hydrazine This compound was prepared fromdimethylaminoacetal and 1,2,3,4-tetrahydroisoquinolinoethyl hydrazine inthe manner described in Examples 1 and 2; B.P. 150 C. (1.2 mm.). Yield,6%; N 1.5572.

A'nalysis.Calcd. for C H N N (titratable), 10.68. Found: N, 10.89.

EXAMPLE EXAMPLE 9 N-(3-Hydr0xypipeidino)Ethyl-N'-(Pyrrolidino- Thefollowing compounds were also prepared by the ethyl)Hydrazine 25described procedures: This compound was prepared from the ethylidenederiv- Am (CH NHNH(CH Am Percent N Compound Am; Am, m n ND!" B.P.,C./mm.

Calcd. Found 1 N NMQ, 2 2 1.4870 9.7 0.7 13.98 14.12

2 EnN NMe 2 2 1.4024 70 000 13.84 13.81

2 3 o N- NMQZ 2 2 1. 4874 105 0025 12. 95 12.99

4 CHzN- NMo; 2 2 1.5191 125 009 11.19 11.18

j 5 N mm, 2 2 1.4836 100 0. 02 12.27 12.08

(E113 9 N- NMe 2 2 1. 4805 s5-00 0.03 12.27 12.21

7 H3CN N- NMcz 2 2 1.4910 100-110 009 12.21 11.99

8 NMei 2 2 1.4843 92-99/025 13. 07 12. 90

9 Me N- NMeg 2 3 ative in Example 4 by the procedure described in Ex-EXAMPLE 10 ample 2 except that tetrahydrofuran was used as a solventN-(Dimethylaminoethyl)-N'-(Piperidin0-ethyl) for the reduction; B.P.145-152 (0.08 mm). Yield, 51%; 60 Hydrazine Dimethiodide Analysis.Calcd.for C H N N (titratable) 16.38. Found: N, 15.49.

EXAMPLE 6 N- (3-H ydroxypiperidino) Ethyl-N (M orpholinoethyl )H ydrazz'ne N (titratable) To a solution containing 5.7 gm. (0.04 mole) of methyliodide in 20 ml. of acetone was added 2.14 gm. (0.01 mole) of the base.The mixture was refrigerated and the acetone decanted from the insolubleoil. Crystallization occurred following the addition of 30 ml. of ethylalcohol. The product was isolated by filtration and washed with anether-alcoho1 mixture. Yield, 2.27 gm. (45.6%); MP. 144-146 C.

Analysis.Ca1cd. for C H I N N (titratable) 5.62; I, 50.74. Found: N,5.43; I, 50.37.

EXAMPLE 11 N -Dimethylamin0ethyl-N -2 [4-( 1 -M ethyl -PiperazinoJEthylHydrazz'ne Trimaleate To a solution of 4.64 gm. (0.04 mole) of maleicacid in 30 ml. of absolute ethanol was added a solution containing 2.29gm. (0.01 mole) of the base in 30 ml. of anhydrous ether. The whitesolid was isolated by filtration and washed with 1:1 ethanol-ether;yield, 5.31 g. The solid was t-riturated with 25 ml. of warm absoluteethanol and the mixture refrigerated. The purified solid was isolated byfiltration. Yield, 5.15 g. (89%); M.P. 117-l20 C.

Analysis.-Calcd. for C I-1 N O N (titratable), 7.33. Found: N, 7.52.Maleic acid content calcd.: 60.29. Found 60.13.

EXAMPLE 12 N (3 Hydr0xypiperidin0)Ethyl N Morpholinoethyl HydrazineTrimaleate A trimaleate salt was prepared in 1:1 ethanol-ether.

Yield, 75%; M.P. 115-117.

Analysis.--Calcd. for C H N O N (titratable), 6.77. Neutral equiv; 103.Found: N, 6.97; NE. 100.

EXAMPLE 13 N (3 Hydroxypiperidinoethyl) N (1 Methyl 4 Piperazinoethyl)Hydmzine T etramaleate The tetramaleate salt was prepared in absoluteethanol; M.P. 110-1 C. (dec.).

Yield, 76%.

Analysis.--Calcd. for C30H47N5O17I N, 7.48. Neutral equiv.: 93.7. Found:-N, 7.29. Neutral equiv. 93.1.

EXAMPLE 14 N (2 Dimethylaminoethyl) N Formyl N- (Pyrrolidz'noethyl)Hydrazine A mixture containing 32 gm. of'N-(dimethylaminoethyl)-N-(pyrrolidinoethyl) hydrazine and 120 gm. ofethyl formate was refluxed for 24 hours. The product was isolated byfractional distillation; B.P. 127-l29 C.

(0.6 mm); N 1.4950.

Yield, 14.9 g. (41%).

Analysis.'Calcd. for C -I-I N O: N (titratable), 12.27. Found: N, 12.00.

EXAMPLE 15 N (Dimelhylaminoethyl) N Methyl N- Pyrrolz'dinoethyl)Hydrazine The formyl derivative of Example 14 was reduced with litihumaluminum hydride in anhydrous ether as described in Example 2; RP. 83 C.(0.25 mm); N 1.4735.

Yield, 72%.

Analysis.-Calcd. for C H N N (titratable), 13.07. Found: N, 13.33.

The trimaleate salt was prepared in a mixture of ethanol and ether; M.P.138 C.

Analysis.Calcd. for C lH N O N (titratable), 7.47. Maleic acid content,61.89. Found: N, 7.25. Maleic acid content, 61.53.

EXAMPLE 16 Methiode salts of some of the compounds of Example 9 werealso prepared and the following data obtained:

Percent N Percent I Compound M.P. C.

Calcd. Found Calcd. Found 1 Very hygroscopic.

10 EXAMPLE 17 Maleate salts of some of the compounds of Example 9 werealso prepared and the following data obtained:

Various changes and modifications of the invention can be made and, tothe extent that such variations incorporate the spirit of thisinvention, they are intended to be included within the scope of theappended claims.

What is claimed is:

1. A member of the group consisting of compounds of the formulae whereinA is a member of the group consisting of and (CHz) mIIINH (CH2) n+1-wherein m is an integer from 2 to 10, n is an integer from 1 to 9, R andR are lower alkyl,

represents a member of the group consisting of pyrrolidino, piperidino,4-lower alkyl-piperazino, morpholino, S-hydroxypiperidino and1,2,3,4-tetrahydroisoquinolino, and R is a member of the groupconsisting of hydrogen and lower alkyl groups, and nontoxicpharmaceutically acceptable acid addition salts thereof.

2. N dimethylarninoethyl N pyrrolidinoethyl hydrazine.

3. N (3 hydroxypiperidino)ethyl N dimethylaminoethyl hydrazine.

4. N (3 hydroxypiperidino)ethyl N morpholinoethyl hydrazine.

5. -N (3 hydroxypiperidino)ethyl N (l methyl- 4-piperazinoethyl)hydrazine.

6. N dimethylaminoethyl N (1,2,3,4 tetrahydroisoquinolino)ethylhydrazine.

7. N diethylaminoethyl N pyrrolidinoethyl hydrazine.

8. N dimethylaminoethyl N morpholinoethyl hydrazine.

References Cited in the file of this patent UNITED STATES PATENTS2,830,050 Biel Apr. 8, 1958 2,948,731 De Stevens Aug. 9, 1960 2,951,078Biel Aug. 30, 1960

1. A MEMBER OF THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULAE
 8. N -DIMETHYLAMINOETHYL - N'' - MORPHOLINOETHYL HYDRAZINE.